三氯乙酰亚胺酯法合成紫草素-1'-<i>O-β</i>-D-吡喃葡萄糖苷

李龙珠; 张玉心; 吴成柱; 李红梅; 马涛

doi:10.13898/j.cnki.issn.1000-2200.2021.03.030

三氯乙酰亚胺酯法合成紫草素-1'-O-β-D-吡喃葡萄糖苷

Synthesis of shikonin-1'-O-β-D-glucopyranoside by the trichloroacetimide ester method

摘要

摘要:
目的采用三氯乙酰亚胺酯法合成紫草素-1'-O-β-D-吡喃葡萄糖苷。
方法以β-D-吡喃葡萄糖为起始原料制得糖基供体2，3，4，6-四-O-乙酰基-β-D-吡喃半乳糖酰基2，2，2-三氯乙酰亚胺酯，然后与紫草素反应得1-（1-（5，8-二羟基-1，4-萘醌-2-基）-4-甲基-3-戊烯氧基）-2，3，4，6-四-O-乙酰基-β-吡喃葡萄糖苷，最后在甲醇钠/甲醇体系下醇解脱去乙酰基得到目标化合物，采用核磁共振波谱（NMR）和电喷雾-质谱（ESI-MS）表征其结构。
结果NMR和ESI-MS鉴定目标化合物为紫草素-1'-O-β-D-吡喃葡萄糖苷。三氯乙酰亚胺酯法合成紫草素-1'-O-β-D-吡喃葡萄糖苷总收率为38.9%，HPLC测定纯度为96.7%。
结论本方法合成紫草素-1'-O-β-D-吡喃葡萄糖苷具有高立体选择性和高收率的优点，为紫草素糖基化修饰产物的化学合成提供了参考。

Abstract:
ObjectiveTo synthesize shikonin-1'-O-β-D-glucopyranoside by the trichloroacetimide ester method.
MethodsThe glycosyl donor 2, 3, 4, 6-tetra-O-acetyl-β-D-galactopyranoyl-2, 2, 2-trichloroacetyl was prepared from β-D-glucopyranose as starting material.The imine ester was then reacted with shikonin to obtain1-(1-(5, 8-dihydroxy-1, 4-naphthoquinone-2-yl)-4-methyl-3-pentenoxy)-2, 3, 4, 6-tetra-O-acetyl-β-glucopyranoside, and finally alcoholyzed to remove the acetyl group under the sodium methoxide/methanol system to obtain the target compound.The structure of the target compound was elucidated by nuclear magnetic resonance spectroscopy (NMR) and electrospray ionization mass spectrometry (ESI-MS).
ResultsThe target compound was identified as shikonin-1'-O-β-D-glucopyranoside by NMR and ESI-MS.The total yield of shikonin-1'-O-β-D-glucopyranoside synthesized by the trichloroacetimide ester method was 38.9%, and the purity determined by HPLC was 96.7%.
ConclusionsThe method has the advantages of high stereoselectivity and high yield.It can be used for the synthesis of shikonin-1'-O-β-D -glucopyranoside, and provide a reference for the chemical synthesis of shikonin glycosylation modified products.

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